Size-dependent optical properties of periodic arrays of semiconducting nanolines.

We study the size-dependent optical properties of periodic arrays of semiconducting nanolines in the near-infrared to near-ultraviolet spectral range, where the absorption of the semiconductor increases. Using band structure calculations, we demonstrate that specific dimensions allow the slow down of the light, resulting in an enhanced absorption as compared to bulk material once the extinction coefficient of the semiconductor becomes comparable to its refractive index. Further, the refractive properties of the arrays can be tailored beyond the values of the constituting materials when the extinction coefficient of the semiconductor exceeds its refractive index. To confirm our theoretical findings, we propose a simple semi-analytical model for the light interactions with such structures and validate it with experimental reflectance spectra collected on arrays for the next-generation transistors.

Quantum-dot light-emitting diode with ultrathin Au electrode embedded in solution-processed phosphomolybdic acid.

We proposed to exploit phosphomolybdic acid (PMA) as a cost-efficient MoO x source for combined spin-coating/sputtering/spin-coating deposition of a MoO x /Au/MoO x (MAM) composite electrode. The bottom PMA layer provides perfect wetting conditions for ultrathin Au film sputtering and prevents the formation of gold islands on the glass surface, while the top PMA layer helps to reduce light reflection. By optimizing the thickness of ultrathin Au films and PMA layers, we achieved maximum transmittance of 79% at 550 nm and a sheet resistance of only 22 Ω sq-1 which is comparable to the resistance of ITO substrates (20 Ω sq-1). MAM multilayer was explored both as a transparent electrode and as a hole injection layer (HIL) to eliminate ITO and PEDOT:PSS from solution-processed quantum-dot light-emitting diodes (QLEDs). The fabricated MAM-based QLED shows a peak external quantum efficiency (EQE) of 2.7% and maximum brightness of 12 000 cd m-2 at 7 V. By performing bending tests of the polyethylene (PET) substrate coated with MAM electrode, we demonstrate that it is also a promising candidate for flexible transparent optoelectronics.

The effect of core and lanthanide ion dopants in sodium fluoride-based nanocrystals on phagocytic activity of human blood leukocytes.

Sodium fluoride-based ß-NaLnF4 nanoparticles (NPs) doped with lanthanide ions are promising materials for application as luminescent markers in bio-imaging. In this work, the effect of NPs doped with yttrium (Y), gadolinium (Gd), europium (Eu), thulium (Tm), ytterbium (Yb) and terbium (Tb) ions on phagocytic activity of monocytes and granulocytes and the respiratory burst was examined. The surface functionalization of <10-nm NPs was performed according to our variation of patent pending ligand exchange method that resulted in meso-2,3-dimercaptosuccinic acid (DMSA) molecules on their surface. Y-core-based NCs were doped with Eu ions, which enabled them to be excited with UV light wavelengths. Cultures of human peripheral blood (n = 8) were in vitro treated with five different concentrations of eight NPs for 24 h. In summary, neither type of nanoparticles is found toxic with respect to conducted test; however, some cause toxic effects (they have statistically significant deviations compared to reference) in some selected doses tested. Both core types of NPs (Y-core and Gd-core) impaired the phagocytic activity of monocytes the strongest, having minimal or none whatsoever influence on granulocytes and respiratory burst of phagocytic cells. The lowest toxicity was observed in Gd-core, Yb, Tm dopants and near-infrared nanoparticles. Clear dose-dependent effect of NPs on phagocytic activity of leukocytes and respiratory burst of cells was observed for limited number of samples.

Interface Intermixing in Type II InAs/GaInAsSb Quantum Wells Designed for Active Regions of Mid-Infrared-Emitting Interband Cascade Lasers.

The effect of interface intermixing in W-design GaSb/AlSb/InAs/Ga0.665In0.335AsxSb1 - x/InAs/AlSb/GaSb quantum wells (QWs) has been investigated by means of optical spectroscopy supported by structural data and by band structure calculations. The fundamental optical transition has been detected at room temperature through photoluminescence and photoreflectance measurements and appeared to be blueshifted with increasing As content of the GaInAsSb layer, in contrast to the energy-gap-driven shifts calculated for an ideally rectangular QW profile. The arsenic incorporation into the hole-confining layer affects the material and optical structure also altering the InAs/GaInAsSb interfaces and their degree of intermixing. Based on the analysis of cross-sectional transmission electron microscopy images and energy-dispersive X-ray spectroscopy, we could deduce the composition distribution across the QW layers and hence simulate more realistic confinement potential profiles. For such smoothed interfaces that indicate As-enhanced intermixing, the energy level calculations have been able to reproduce the experimentally obtained trend.

Ghost Branch Photoluminescence From a Polariton Fluid Under Nonresonant Excitation.

An expanding polariton condensate is investigated under pulsed nonresonant excitation with a small laser pump spot. Far above the condensation threshold we observe a pronounced increase in the dispersion curvature, with a subsequent linearization of the spectrum and strong luminescence from a ghost branch orthogonally polarized with respect to the linearly polarized condensate emission. Polarization of both branches is understood in terms of spin-dependent polariton-polariton scattering. The presence of the ghost branch has been confirmed in time-resolved measurements. The effects of disorder and dissipation in the photoluminescence of polariton condensates and their excitations are discussed.

Submonolayer Uniformity of Type II InAs/GaInSb W-shaped Quantum Wells Probed by Full-Wafer Photoluminescence Mapping in the Mid-infrared Spectral Range.

The spatial uniformity of GaSb- and InAs substrate-based structures containing type II quantum wells was probed by means of large-scale photoluminescence (PL) mapping realized utilizing a Fourier transform infrared spectrometer. The active region was designed and grown in a form of a W-shaped structure with InAs and GaInSb layers for confinement of electrons and holes, respectively. The PL spectra were recorded over the entire 2-in. wafers, and the parameters extracted from each spectrum, such as PL peak energy position, its linewidth and integrated intensity, were collected in a form of two-dimensional spatial maps. Throughout the analysis of these maps, the wafers' homogeneity and precision of the growth procedure were investigated. A very small variation of PL peak energy over the wafer indicates InAs quantum well width fluctuation of only a fraction of a monolayer and hence extraordinary thickness accuracy, a conclusion further supported by high uniformity of both the emission intensity and PL linewidth.

Facile synthesis of phosphine free ultra-small PbSe nanocrystals and their light harvesting studies in ETA solar cells.

Ultra-small PbSe nanocrystals (NCs) were synthesized via a 'one-pot' approach in olive oil as the reaction medium and capping agent. The optical spectra showed discernible blue shifts in the absorption band edges (570-780 nm) due to strong quantum confinement effects and photoluminescence (PL) spectra showed significant strong emission peaks in the range of 780-850 nm. The broad peaks in the powder X-ray diffraction (p-XRD) pattern indicate the ultra-small size of the as-prepared NCs. These NCs were used to construct an extremely thin absorber (ETA) solar device after surface modification. The preliminary results indicate their potential as light harvesting entities in nanostructure based solar cells.

Hydrophobic sodium fluoride-based nanocrystals doped with lanthanide ions: assessment of in vitro toxicity to human blood lymphocytes and phagocytes.

In vitro immunotoxicity of hydrophobic sodium fluoride-based nanocrystals (NCs) doped with lanthanide ions was examined in this study. Although there is already a significant amount of optical and structural data on NaYF4 NCs, data on safety assessment are missing. Therefore, peripheral whole blood from human volunteers was used to evaluate the effect of 25 and 30 nm hydrophobic NaYF4 NCs dissolved in cyclohexane (CH) on lymphocytes, and of 10 nm NaYF4 NCs on phagocytes. In the concentration range 0.12-75 µg cm(-2) (0.17-106 µg ml(-1) ), both 25 and 30nm NaYF4 NCs did not induce cytotoxicity when measured as incorporation of [(3) H]-thymidine into DNA. Assessment of lymphocyte function showed significant suppression of the proliferative activity of T-lymphocytes and T-dependent B-cell response in peripheral blood cultures (n = 7) stimulated in vitro with mitogens phytohemagglutinin (PHA) and pokeweed (PWM) (PHA > PWM). No clear dose-response effect was observed. Phagocytic activity and respiratory burst of leukocytes (n = 5-8) were generally less affected. A dose-dependent suppression of phagocytic activity of granulocytes in cultures treated with 25 nm NCs was observed (vs. medium control). A decrease in phagocytic activity of monocytes was found in cells exposed to higher doses of 10 and 30 nm NCs. The respiratory burst of phagocytes was significantly decreased by exposure to the middle dose of 30 nm NCs only. In conclusion, our results demonstrate immunotoxic effects of hydrophobic NaYF4 NCs doped with lanthanide ions to lymphocytes and to lesser extent to phagocytes. Further research needs to be done, particularly faze transfer of hydrophobic NCs to hydrophilic ones, to eliminate the solvent effect.

Visualization of melanoma tumor with lectin-conjugated rare-earth doped fluoride nanocrystals.

AIM: To develop specific fluorescent markers for melanoma tumor visualization, which would provide high selectivity and reversible binding pattern, by the use of carbohydrate-recognizing proteins, lectins, combined with the physical ability for imaging deep in the living tissues by utilizing red and near infrared fluorescent properties of specific rare-earth doped nanocrystals (NC). METHODS: B10F16 melanoma cells were inoculated to C57BL/6 mice for inducing experimental melanoma tumor. Tumors were removed and analyzed by lectin-histochemistry using LABA, PFA, PNA, HPA, SNA, GNA, and NPL lectins and stained with hematoxylin and eosin. NPL lectin was conjugated to fluorescent NaGdF4:Eu(3+)-COOH nanoparticles (5 nm) via zero length cross-linking reaction, and the conjugates were purified from unbound substances and then used for further visualization of histological samples. Fluorescent microscopy was used to visualize NPL-NaGdF4:Eu(3+) with the fluorescent emission at 600-720 nm range. RESULTS: NPL lectin selectively recognized regions of undifferentiated melanoblasts surrounding neoangiogenic foci inside melanoma tumor, PNA lectin recognized differentiated melanoblasts, and LCA and WGA were bound to tumor stroma regions. NPL-NaGdF4:Eu(3+) conjugated NC were efficiently detecting newly formed regions of melanoma tumor, confirmed by fluorescent microscopy in visible and near infrared mode. These conjugates possessed high photostability and were compatible with convenient xylene-based mounting systems and preserved intensive fluorescent signal at samples storage for at least 6 months. CONCLUSION: NPL lectin-NaGdF4:Eu(3+) conjugated NC permitted distinct identification of contours of the melanoma tissue on histological sections using red excitation at 590-610 nm and near infrared emission of 700-720 nm. These data are of potential practical significance for development of glycans-conjugated nanoparticles to be used for in vivo visualization of melanoma tumor.

Time-resolved photoluminescence studies of annealed 1.3-µm GaInNAsSb quantum wells.

Time-resolved photoluminescence (PL) was applied to study the dynamics of carrier recombination in GaInNAsSb quantum wells (QWs) emitting near 1.3 µm and annealed at various temperatures. It was observed that the annealing temperature has a strong influence on the PL decay time, and hence, it influences the optical quality of GaInNAsSb QWs. At low temperatures, the PL decay time exhibits energy dependence (i.e., the decay times change for different energies of emitted photons), which can be explained by the presence of localized states. This energy dependence of PL decay times was fitted by a phenomenological formula, and the average value of E0, which describes the energy distribution of localized states, was extracted from this fit and found to be smallest (E0 = 6 meV) for the QW annealed at 700°C. In addition, the value of PL decay time at the peak energy was compared for all samples. The longest PL decay time (600 ps) was observed for the sample annealed at 700°C. It means that based on the PL dynamics, the optimal annealing temperature for this QW is approximately 700°C.

NaYF4 nanocrystals with TOPO ligands: synthesis-dependent structural and luminescent properties.

A comprehensive characterization of NaYF4 nanocrystals synthesized in trioctylphosphine oxide has been reported in order to present an effective method of monodisperse, small, hexagonal nanocrystal synthesis in a high boiling organic solvent via a co-thermolysis pathway. We observed the influence of temperature, Na/Y precursors ratio and time of the synthesis on the nanocrystals size, shape and crystal structure. For that purpose, we characterized the structure of as-synthesized nanocrystals by X-ray diffraction and transmission electron microscopy. Moreover, all nanocrystals were doped with Eu(3+) ions, which were used as an optical crystal field probe. We applied photoluminescence, PL excitation and absorbance spectra to determine the influence of crystal symmetry, surface to volume ratio and ligands on the optical properties of doped Eu(3+) ions. It was found that trioctylphosphine oxide reduces the free-energy barrier and stimulates the NaYF4 crystallization in the hexagonal phase, even at relatively low temperature. A similar effect was observed when the excess of sodium trifluoroacetate precursors was used. Moreover, the presented nanocrystal evolution within synthesis time confirmed that at suitable conditions NaYF4 crystallized in the hexagonal phase within less than 5 min. Optical spectroscopy investigations confirmed the high quality of small ß-NaYF4:Eu(3+) nanocrystals, which are promising candidates for e.g. optical markers in the visible wavelength range.

On the origin of emission and thermal quenching of SRSO:Er3+ films grown by ECR-PECVD.

Silicon nanocrystals embedded in a silicon-rich silicon oxide matrix doped with Er3+ ions have been fabricated by electron cyclotron resonance plasma-enhanced chemical vapor deposition. Indirect excitation of erbium photoluminescence via silicon nanocrystals has been investigated. Temperature quenching of the photoluminescence originating from the silicon nanocrystals and the erbium ions has been observed. Activation energies of the thermally activated quenching process were estimated for different excitation wavelengths. The temperature quenching mechanism of the emission is discussed. Also, the origin of visible emission and kinetic properties of Er-related emission have been discussed in details.

Correlation between matrix structural order and compressive stress exerted on silicon nanocrystals embedded in silicon-rich silicon oxide.

Silicon nanocrystals embedded in a silicon oxide matrix were deposited by radio frequency reactive magnetron sputtering. By means of Raman spectroscopy, we have found that a compressive stress is exerted on the silicon nanocrystal cores. The stress varies as a function of silicon concentration in the silicon-rich silicon oxide layers varies, which can be attributed to changes of nanocrystal environment. By conducting the Fourier transform infrared absorption experiments, we have correlated the stresses exerted on the nanocrystal core to the degree of matrix structural order. PACS: 78.67.Bf, 78.67.Pt, 73.63.Bd, 78.47.D, 74.25.Nd.

On the nature of carrier relaxation and ion-ion interactions in ultrasmall ß-NaYF4:Eu3+ nanocrystals--effect of the surface.

The purely hexagonal phase of ultrasmall (~10 nm) NaYF(4) nanocrystals (NCs), containing different Eu concentrations, has been obtained by a modified co-thermolysis method. Detailed investigations of the excitation and relaxation mechanisms of the Eu ions in such NCs are reported. Based on the photoluminescence excitation, absorbance, photoluminescence and emission decay times measured as a function of the excitation wavelengths, it has been shown that two Eu sites with different excitation and relaxation characteristics are present in the case of ultrasmall NaYF(4) NCs. It has been shown that, when the Eu concentration increases, strong ion-ion interactions influence the relaxation phenomena in Eu ions, changing their optical properties. Moreover, these ion-ion interactions enable connections between the surface ions and the internal ones via energy transfer from the surface to the NCs core. Furthermore, it has been proposed that the different kinetic properties of the surface Eu ions are mainly caused by the formation of a charge transfer state between the ions and ligand groups attached to the NCs surface.

Controlled synthesis of tuned bandgap nanodimensional alloys of PbS(x)Se(1-x).

Truly alloyed PbS(x)Se(1-x) (x = 0-1) nanocrystals (∼5 nm in size) have been prepared, and their resulting optical properties are red-shifted systematically as the sulfur content of the materials increases. Their optical properties are discussed using a modified Vegard's approach and the bowing parameter for these nanoalloys is reported for the first time. The alloyed structure of the nanocrystals is supported by the energy-filtered transmission electron microscope images of the samples, which show a homogeneous distribution of sulfur and selenium within the nanocrystals. X-ray photoelectron spectroscopy studies on ligand-exchanged nanocrystals confirmed the expected stoichiometry and various oxidized species.